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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >The Role of Phosphorus Dioxide in the H + OH Recombination Reaction: Ab Initio Quantum Chemical Computation of Thermochemical and Rate Parameters
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The Role of Phosphorus Dioxide in the H + OH Recombination Reaction: Ab Initio Quantum Chemical Computation of Thermochemical and Rate Parameters

机译：二氧化磷在H + OH重组反应中的作用：从头算热化学和速率参数的量子化学计算

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A theoretical investigation of the effects of PO_2 on the H + OH radical recombination reaction is reported. The focus of the study is the computation of rate coefficients by ab initio quantum chemical and RRKM methods for the H + PO_2 and OH + PO_2 recombination reactions and for the H + HOPO → H_2 + PO_2, OH + H_2 → H + H_2O, and H + HOPO_2 → H_2O + PO_2 abstraction reactions, which constitute a catalytic pathway for the h + oh recombination reaction (Twarowski, A. Combust. Flame 1993, 94, 91). These are a subset of Twarowski's reaction model (Twarowski, A. Combust. Flame 1995, 102, 41) that consists of 175 individual reactions and includes 17 phosphorus-containing molecules. The thermochemistry of this complete reaction model was computed using the Gaussian methods: G2, G3, and G3X. While G3X was found to be superior to G2 and G3 for the prediction of heats of formation of phosphorus-containing molecules, it underestimates the heat of formation of HOPO_2 by at least 3.6 kcal mol~(-1), when compared with the extensive coupled cluster computations of Bauschlicher (Bauschlicher, C. W., Jr. J. Phys. Chem, 1999, 103, 11126). Consequently, the rate coefficients reported in this work are based on Bauschlicher's thermochemical data PO_2, HOPO, and HOPO_2. The computed rate coefficients are consistent with the available experimental data and the results of modeling studies by Twarowski (Twarowski, A. Combust. Flame 1995, 102, 41) and Korobeinichev et al. (Korobeinichev, O. P.; Ilyin, S. B.; Bolshova, T. A.; Shvartsberg, V. M.; Chernov, A. A. Combust. Flame 2001, 125, 744). The recombination reactions are found to be substantially into the fall-off region at near atmospheric pressures.
机译：报道了PO_2对H + OH自由基重组反应影响的理论研究。研究的重点是通过从头开始的量子化学和RRKM方法计算H + PO_2和OH + PO_2重组反应以及H + HOPO→H_2 + PO_2，OH + H_2→H + H_2O和H + HOPO_2→H_2O + PO_2提取反应，构成h + oh重组反应的催化途径（Twarowski，A。Combust。Flame 1993，94，91）。这些是Twarowski反应模型的子集（Twarowski，A.Combust.Flame 1995，102，41），它由175个独立反应组成，包括17个含磷分子。使用Gaussian方法（G2，G3和G3X）计算此完整反应模型的热化学。虽然在预测含磷分子形成热方面，G3X优于G2和G3，但与广泛耦合相比，它低估了HOPO_2形成热至少3.6 kcal mol〜（-1）。博士伦的聚类计算（Bauschlicher，CW，Jr. J. Phys。Chem，1999，103，11126）。因此，这项工作中报告的速率系数是基于Bauschlicher的热化学数据PO_2，HOPO和HOPO_2。计算出的速率系数与可用的实验数据和Twarowski（Twarowski，A. Combust。Flame 1995，102，41）和Korobeinichev等人的建模研究结果一致。 （Korobeinichev，O. P .; Ilyin，S. B .; Bolshova，T.A .; Shvartsberg，V.M .; Chernov，A.A. Combust。Flame 2001，125，744）。发现重组反应在接近大气压下基本上进入了脱落区域。

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